Fuel additive

ABSTRACT

A composition and method for improving the performance, and thus, also the fuel economy, of an internal combustion engine by introducing a fuel additive into the engine&#39;s fuel supply to enhance fuel lubricity. The composition can feature a mixture of esters, glycol ether, and a solvent. The mixture of esters can include adipate esters, azelate esters, dodecanedioate esters, sebacate esters, or phthalate esters. Esters that may be used to create the composition can include a mixture of two or more adipate esters such as, for example, an adipic acid ester, a glutaric acid ester, and a succinic acid ester. The composition can further feature a smoke suppressant that can be an organometallic soap. The organometallic soap can be an iron salt of a fatty acid such as, for example, ferrocene. The composition can be used as a combustion modifier fuel additive and as a lubricating oil.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of and claims the priorityfrom U.S. nonprovisional patent application Ser. No. 11/846,994 filedAug. 29, 2007. The foregoing application is incorporated in its entiretyherein by reference.

FIELD OF THE INVENTION

The invention relates to compositions and methods for improving engineperformance. More particularly, the invention relates to compositionsand methods for improving engine performance by increasing the lubricityof fuel and for lubricating two or more parts in frictional contact.

BACKGROUND

Current government regulations related to hydrocarbon fuels require lowsulfur content. Certain chemical processes can be used to reduce theoverall sulfur content of commercially available fuels so as to decreasethe environmental impact of fossil fuel combustion. The removal ofsulfur compounds from fuels has resulted in a corresponding decrease inthe incidence of acid rain, acidic fogs and other environmentallyharmful pollution-linked weather phenomena. However, the presence ofsulfur in fuels also imparts a beneficial lubricating effect to the fuelthat reduces friction within a combustion engine. Sulfur compoundspresent in fuel impart a lubricating effect to the exposed wearingsurfaces of an internal combustion engine which are exposed tofrictional forces. The lubricity of the fuel is directly linked toengine performance, and therefore, also to fuel efficiency. Removal ofsulfur-containing compounds from fuel sources increases the degree offrictional wearing experienced by exposed surfaces of the internalcombustion engine and its parts. While providing a benefit to theenvironment in some regards, the elimination of sulfur-containingcompounds from modern fuels has decreased the lubricity of these fuels,which has caused a corresponding decline in engine performance and fuelefficiency of automobile engines and other internal combustion engines.These effects may increase the amount of fossil fuels used by consumers,and therefore, may contribute to further increases in the amount of fuelcombustion by-products that are released into the atmosphere as airborneemissions. Increases in the amount of emissions released by automobilesmay be linked to the occurrence of smog, global warming, and otherenvironmental harm.

Fuel additives have also incorporated solvents intended to clean theinternal surfaces of internal combustion engines. These conventionalfuel additives often include hazardous synthetic compounds that are notbiodegradable and which actually increase the amount of pollutionreleased into the environment as a byproduct of fossil fuel combustion.Due to the toxicity of their ingredients, the use of such conventionalfuel additives may offset any advantages obtained through burning of abiofuel (e.g., ethanol or bio-diesel) as a fuel source.

Soy-based and petroleum-based lubricants used as fuel additives and aslubricating oils have only a limited period of time for effectivenesswhen used. As a result of the short effective life of conventionallubricants, they are not ideal for use as fuel additives to providelubricity in internal combustion engines or to be used as lubricatingoils on moving parts. Conventional lubricants and solvents are oftencomposed of toxic compounds that pose hazards to the environment and itsinhabitants.

SUMMARY

The invention relates to a composition that can be used as a fueladditive that can function as a combustion modifier and as a lubricatingoil. The composition is created from a mixture of ingredients that caninclude one or more esters, glycol ether, and a solvent. The compositioncan also feature a smoke suppressant. The smoke suppressant can be anorganometallic soap such as, for example, a metal salt of an alkanoicacid. In one embodiment, the organometallic soap can be ferrocene. Theglycol ether and metallic smoke suppressants of the composition can actto reduce smoke and soot emissions produced by fuel combustion. Theingredients of the composition can be bio-based compounds produced fromgrains. The composition can be used as a combustion modifying fueladditive and as a lubricant on metals, alloys, elastomer materials,plastics, coatings, finishes, and seals.

As a fuel additive, the composition provides several advantages whenadded to the fuel supply of a combustion engine. The fuel additive actsas a solvent. The fuel additive can improve the performance of theengine. The fuel additive can also improve fuel economy (or fuelmileage) and reduce emissions that are harmful to the environment. Oncemixed with the fuel supply introduced into a combustion engine, the fueladditive can improve engine performance by enhancing the lubricity ofthe fuel. The fuel additive affects these improvements in engineperformance due, in part, to its lower volatility, excellent lubricity,and its detergent and dispersant qualities. Many of these engineperformance-enhancing characteristics are connected to the polarity ofthe ester molecules present in the composition.

The composition's ester molecules exhibit an intermolecular attraction,which is connected to the polarity of the ester molecules. Thisintermolecular attraction requires more energy in the form of heat toovercome the linkages between molecules so that the esters can changestate from a liquid to a gas. At a given molecular weight or viscosity,the esters have a low vapor pressure that imbues the composition with ahigher flash point and lower rate of evaporation, properties that arebeneficial for a lubricant. Lubricants that evaporate quickly havelittle time to impart their lubricating properties to an engine. Thenon-evaporative nature of the composition extends its usefulness as alubricant by ensuring that its lubricating effects last longer than whatis characteristic for a petroleum or soy-based lubricant. Thecompositions of the invention can include esters that exhibit theformation of many linkages between ester molecules so that the flashpoint of the composition remains high and its volatility is low to allowthe composition more time to lubricate the engine parts.

The polarity of the composition's ester molecules also causes themolecules to be attracted to positively-charged metal surfaces. Whenintroduced with the fuel supply into the combustion chamber of aninternal combustion engine, the ester molecules are attracted to themetal surfaces inside the engine and form a film or coating. Thelinkages between ester molecules caused by intermolecular attractiveforces renders the film more difficult to penetrate than that oflubricants because of the additional energy required to evaporate thecomposition. Thus, the composition produces a stronger film withlubricity properties that are enhanced compared to those of conventionallubricating fuel additives. In turn, the additional lubricity impartedto the fuel by the composition decreases energy consumption by theengine by lubricating the internal engine parts which operate moreefficiently than when affected by frictional forces that can degrade theengine's performance.

In addition, the polarity of the composition's ester molecules enhancesthe composition's effectiveness as a detergent and dispersant. Thecomposition's esters provide the composition with solvent propertiespermitting the composition to be used to dissolve and disperse oilby-products of fossil fuel combustion. By solubilizing the oilby-products, the by-products can be burned away during combustion ratherthan being deposited on the internal surfaces of the combustion engineas sludge or varnish, which could diminish engine performance. Thecomposition can be used to quickly and effectively clean metallicsurfaces by removing dirt and grease. Therefore, the composition alsoimproves engine performance by improving the solvent and detergentproperties of the fuel to which it is added, thereby resulting incleaner engine operation.

As a lubricating oil, the composition exhibits the aforementionedqualities that are advantageous when the composition is used as a fueladditive or as a lubricating oil. Because the composition is bio-based(made from, for example, soy-based products), the composition is saferfor use than many conventional lubricating oils and fuel additives thatcan contain harsh artificial chemicals that are damaging to theenvironment. In addition to its long-lasting lubrication effects, thecomposition also exhibits superior water displacement and anti-corrosionproperties that can protect metal surfaces against the formation ofrust. By forming a lubricating coating over and displacing water (e.g.,moisture or condensation) from metal surfaces, the composition is ableof preventing corrosion, rust formation, and damaging oxidation effects.The lubricant can be used to lubricate the interface between contactingmetal surfaces. The composition can be used as a penetrating lubricantthat can be used when assembling parts of various types of equipment,e.g., mechanical inventions such as an engine, and also forms aprotective coating over objects, and particularly, over the surface ofmetallic objects. The lubricating oil can also be used to loosencorroded or rusted fittings that are frozen in place.

The composition also provides advantages in that it is created fromnon-toxic ingredients that are environmentally friendly. Conventionalcommercial and industrial fuel additives and lubricants often containtoxic compounds that can damage the environment or which can causedeath, illness, or other adverse health effects among humans and otheranimals exposed to their toxic ingredients. The compositions of thisinvention can be produced using bio-based ingredients and need notinclude artificial compounds that can be toxic and harmful to theenvironment.

The invention also relates to methods for improving engine performanceand fuel economy and reducing harmful emissions associated with thecombustion of fossil fuels, bio-fuels, and other carbon-based fuels bycombustion engines, and particularly, by internal combustion engines.

Because the composition can be created from bio-based sources such as,for example, grains, the composition can be made from renewableresources and reduces the consumption of petroleum and othernon-renewable resources. The composition is also as effective as butless expensive to produce than synthetic lubricants and mineral oils.The bio-based formula of the composition also renders the compositionbiodegradable but resistant to break down at cold temperatures, underheat, and with exposure to heavy loads and moisture.

Yet another advantage of the composition is its load carrying capacitywhich exceeds that of many conventional lubricants and allows thecomposition to exhibit exceptional anti-wear and pressure performance.

Still another advantage of the composition is that metallic salts can beincluded as an environmentally safe ingredient for enhancing the smokesuppressing effects of glycol ethers and to reduce particulateemissions.

Accordingly, the invention can feature a composition for improvingengine performance, the composition comprising a mixture of esters,glycol ether, and a solvent.

In another aspect, the invention can feature the mixture of estersincluding at least two esters selected from among the following: adipateesters, azelate esters, dodecanedioate esters, sebacate esters, andphthalate esters.

In another aspect, the invention can feature the mixture of estersincluding at least two adipate esters.

In another aspect, the invention can feature the at least two adipateesters including an adipic acid ester, a glutaric acid ester, and asuccinic acid ester.

In another aspect, the invention can feature the mixture of estersincluding dimethyl adipate, dimethyl gluctorate, and dimethyl succinate.

In another aspect, the invention can feature a smoke suppressant. Thesmoke suppressant can be an organometallic soap.

The invention also features a composition for improving the combustionefficiency of an internal combustion engine in combusting hydrocarbonfuels. The composition can include a hydrocarbon fuel and a combustionmodifier. The combustion modifier can be an organometallic soap.

In another aspect, the invention can feature the organometallic soapbeing selected from among one or more of the following:cerium-2-ethylhexanoate, cerium octoate, cerium stearate, ceriumnaphthenate, cerium salicylate, cerium carbonate, cerium ammoniate,cerium ureate, cerium nitrate, ferric octoate, ferric-2-ethylhexanoate,ferric stearate, ferric naphthenate, ferric salicylate, ferriccarbonate, diborylated ferrocene, n-butyl ferrocene, 1,1′-dimethylferrocene, benzoyl ferrocene, iron (III) oxide (Fe₂O₃) iron (II, III)oxide (Fe₃O₄), and combinations thereof.

In another aspect, the invention can feature the organometallic soapincluding a compound selected from among the following: cerium octoate,cerium ammoniate, cerium ureate, or cerium-2-ethylhexanoate.

In another aspect, the invention can feature the organometallic soapbeing diborylated ferrocene.

In another aspect, the invention can feature the organometallic soapbeing the reaction product of 1,1′-bis(ethenyl-4-pyridyl)-ferrocene and-1,1′-binaphthol.

In another aspect, the invention can feature the organometallic soapbeing a mixture of diborylated ferrocene and a compound selected fromamong cerium-2-ethylhexanoate or cerium octoate.

In another aspect, the invention can feature the organometallic soapbeing a mixture of diborylated ferrocene and a compound selected fromamong cerium ammoniate or cerium ureate.

In another aspect, the invention can feature the composition furtherincluding a hydrocarbon fuel.

In another aspect, the invention can feature the mixture of estersincluding at least two esters selected from among the following: adipateesters, azelate esters, dodecanedioate esters, sebacate esters, orphthalate esters.

In another aspect, the invention can feature the mixture of estersincluding at least two adipate esters.

In another aspect, the invention can feature the at least two adipateesters including an adipic acid ester, a glutaric acid ester, and asuccinic acid ester.

In another aspect, the invention can feature the smoke suppressant beingan iron salt.

The invention can also feature a composition for improving thecombustion efficiency of an internal combustion engine in combustinghydrocarbon fuels. The composition can include a hydrocarbon fuel, ahydrocarbon carrier, and a combustion modifier. The combustion modifiercan be the reaction product of 1,1′-bis(ethenyl-4-pyridyl)-ferrocene and-1,1′-binaphthol.

In another aspect, the invention can feature the hydrocarbon carrierincluding a compound selected from among one or more of the following:biphenyl, naphthol, beta naphthol, naphthol-2, beta-binaphthol,dicyclopentadiene, beta-binaphthol, dicyclopentadiene, and combinationsthereof.

In another aspect, the invention can feature the hydrocarbon carrierbeing beta-binaphthol.

In another aspect, the invention can feature the hydrocarbon carrierbeing dicyclopentadiene.

Still another method of the invention can be used to introduce into aninternal combustion engine a hydrocarbon fuel and a fuel additive. Thefuel additive can feature a mixture of esters, glycol ether, and asolvent.

Another method of the invention can include the mixture of estersincluding at least two adipate esters. The at least two adipate esterscan be selected from at least two of the following: an adipic acidester, a glutaric acid ester, or a succinic acid ester.

Yet another method of the invention can be used to reduce frictionbetween moving parts. The method can include the step of lubricating theat least two parts that are in frictional contact with a lubricant. Thelubricant can feature a mixture of esters, glycol ether, and a solvent.

Another method of the invention can feature the at least two parts beingmetal parts.

Another method of the invention can feature the metal parts being partsof an internal combustion engine.

Unless otherwise defined, all technical terms used herein have the samemeaning as commonly understood by one of ordinary skill in the art towhich this invention belongs. Although methods and materials similar orequivalent to those described herein can be used in the practice ortesting of the present invention, suitable methods and materials aredescribed below. All publications, patent applications, patents andother references mentioned herein are incorporated by reference in theirentirety. In the case of conflict, the present specification, includingdefinitions will control.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a chart representing fuel pounds per hour measurements for acontrol test in which diesel fuel was combusted in an internalcombustion engine without the addition of a combustion modifier of theinvention.

FIG. 1B is a chart representing measurements of air consumed by fuelcombustion for a control test in which diesel fuel was combusted in theinternal combustion engine without the addition of a combustion modifierof the invention.

FIG. 2A is a chart representing fuel pounds per hour measurements for anexperimental test in which diesel fuel was combusted in an internalcombustion engine to which a combustion modifier of the invention wassupplied.

FIG. 2B is a chart representing measurements of air consumed by fuelcombustion for an experimental test in which diesel fuel was combustedin the internal combustion engine to which a combustion modifier of theinvention was supplied.

DETAILED DESCRIPTION

The invention provides compositions that can be used as fuel additivesor as lubricating oils. Compositions of the invention can be used toimprove the combustion efficiency of an internal combustion engine, andin particular, the internal combustion engine of a vehicle, incombusting hydrocarbon fuels. Compositions of the invention can also beused to reduce friction between two moving parts in frictional contactsuch as, for example, the moving parts of the internal combustionengine. The composition can feature a mixture of esters, glycol ether,and a solvent.

In other embodiments, the composition can also feature a smokesuppressant. The smoke suppressant can be a combustion modifier. Thecombustion modifier can be an organometallic soap.

The mixture of esters can include at least two esters that are adipateesters, azelate esters, dodecanedioate esters, sebacate esters, orphthalate esters.

In an exemplary embodiment, the mixture of esters can include at leasttwo adipate esters. In a most exemplary embodiment, the adipate esterscan be an adipic acid ester, a glutaric acid ester, a succinic acidester, or a combination of one or more of these esters.

In one exemplary embodiment, the mixture of esters of the compositioncan include at least two of dimethyl adipate, dimethyl glutorate, anddimethyl succinate. These esters can be included in the composition inthe ratios described below.

In one embodiment, the composition can include, in percentages byweight, about 0.5-7% dimethyl adipate, about 0.5-10% dimethyl glutorate,about 0-7% dimethyl succinate, about 0.5-7% glycol ether, and about70-95% solvent.

In a more preferred embodiment, the composition can include, inpercentages by weight, about 0.5-5% dimethyl adipate, about 1-9%dimethyl glutorate, about 0-5% dimethyl succinate, about 1-5% glycolether, and about 85-95% solvent.

In a most preferred embodiment, the composition can include, inpercentages by weight, about 1-2% dimethyl adipate, about 4-6% dimethylglutorate, about 0.5-2% dimethyl succinate, about 2-4% glycol ether, andabout 88-92% solvent.

In another exemplary embodiment, the composition can include a smokesuppressant and a mixture of esters of the composition featuring atleast two of dimethyl adipate, dimethyl glutorate, and dimethylsuccinate. For example, in the following embodiments, the smokesuppressant can be the organometallic soap, ferrocene, although anysmoke suppressant described herein can be used. These esters and smokesuppressant can be included in the composition in the ratios describedbelow.

In one embodiment, the composition can include, in percentages byweight, about 0.5-7% dimethyl adipate, about 0.5-10% dimethyl glutorate,about 0-7% dimethyl succinate, about 0.5-7% glycol ether, about 0.5-4%smoke suppressant, and about 70-95% solvent.

In a more preferred embodiment, the composition can include, inpercentages by weight, about 0.5-5% dimethyl adipate, about 1-9%dimethyl glutorate, about 0-5% dimethyl succinate, about 1-5% glycolether, about 1-3% smoke suppressant, and about 85-95% solvent.

In a most preferred embodiment, the composition can include, inpercentages by weight, about 1-2% dimethyl adipate, about 4-6% dimethylglutorate, about 0.5-2% dimethyl succinate, about 2-4% glycol ether,about 1.5-2.5% smoke suppressant, and about 88-92% solvent.

In one example of a composition described herein, the composition caninclude, in percentages by weight, about 1.89% dimethyl adipate, about5.31% dimethyl glutorate, about 1.8% dimethyl succinate, about 3% glycolether, and about 89% solvent.

In another example of a composition described herein, the compositioncan include in percentages by weight, about 2.52% dimethyl adipate,about 7.08% dimethyl glutorate, about 2.4% dimethyl succinate, about 6%glycol ether, about 2.5% ferrocene as the smoke suppressant, and about79.5% solvent.

In another example of a composition contemplated herein, the compositionmay include no solvent, glycol ether, or smoke suppressant but caninclude in percentages by weight, about 4.2% dimethyl adipate, about11.8% dimethyl glutorate, about 4% dimethyl succinate, about 56% methyllaurate, about 22.4% methyl myristate, and about 0.8% methyl palmitate.

Example 1

Tests were conducted to determine the effectiveness of the compositionin improving lubricity of a standard commercial pump diesel fuel thatwould be used to power a diesel-powered internal combustion engine. Thetests were conducted using a high frequency reciprocating rig (HFRR) andASTM D-6079, the standard test method used to evaluate the lubricity ofdiesel fuels in an HFRR. As a diesel fuel standard specification forlubricity, the test used ASTM D-975 as a baseline, i.e., 520 micronsmaximum for the wear scar at 60° C. using the HFRR test method. In anuntreated first sample, the test was performed using a commercial pumpultra low sulfur diesel fuel (ULSD). Using the HFRR and standardspecification described above, the lubricity using the untreated firstsample was determined to be 333 microns. A second sample was prepared byadding one of the compositions described herein above to a commercialpump ultra low sulfur diesel fuel. The test was then performed in theHFRR using this second treated sample, and its lubricity was determinedto be 290 microns. The results of these particular tests showed thatlubricity of a commercial pump ultralow sulfur diesel fuel were improvedsignificantly by adding the composition to the diesel fuel as opposed tousing an untreated diesel fuel.

Hydrocarbon fuels with which the composition can be mixed include, forexample, (1) petroleum-derived fossil fuels such as gasoline, diesel,jet fuel, fuel oil, and kerosene; (2) biofuels such as bioethanol,biodiesel, straight vegetable oils (pure plant oils), and wastevegetable oils; and (3) combinations thereof. The composition can alsobe used in engines that are powered by natural gas.

Example 2

Emissions tests were conducted for one of the compositions describedherein above using two internal combustion engines (a V16 Waukesha™engine and a 2500-hp V16 Caterpillar™ engine, model #3515) powered bynatural gas. Both engines burned approximately 10,000 cubic feet (10 MBTUs) of natural gas per hour, and were running at 1,200 rpm. Comparedwith a control of natural gas and no additive, when the compositiondescribed herein was added to the engines as they burned the naturalgas, NO_(x) and other toxic emissions were reduced substantially from250 ppm to 50 ppm. The test results also showed that fuel consumptionwas reduced by approximately 18% and engine speed was increased from1,200 rpm to 1,400 rpm after the composition was added, therebyresulting in significantly better engine improvement.

In some embodiments, the composition may include more than one smokesuppressant. The smoke suppressants can be metallic smoke suppressantssuch as, for example, metallic salts of alkanoic acid. In an exemplaryembodiment, the smoke suppressant can be an iron salt such as, forexample, an organometallic soap. In another embodiment, the smokesuppressant can be a barium salt. In embodiments in which thecomposition is used as a fuel additive, the composition can furtherinclude a hydrocarbon fuel.

A composition of this invention may also include a hydrocarbon fuel anda combustion modifier that can be an organometallic soap, but no mixtureof esters and no glycol ether. The organometallic soaps described hereinbelow can be used in both compositions that include and those that donot include a mixture of esters and glycol ether.

The smoke suppressant can be an organometallic soap. The organometallicsoap may contain ferric iron or cerium (III). The organometallic soap ofthe combustion modifier can be selected from among the following ferricand cerous organometallic soap compounds: cerium ammoniate, ceriumureate, cerium nitrate, cerium-2-ethylhexanoate, cerium octoate, ceriumstearate, cerium naphthenate, cerium salicylate, cerium carbonate,ferric octoate, ferric-2-ethylhexanoate, ferric stearate, ferricnaphthenate, ferric salicylate, ferric carbonate, diborylated ferrocene,n-butyl ferrocene, 1,1′-dimethyl ferrocene, benzoyl ferrocene, iron(III) oxide (Fe₂O₃), iron (II, III) oxide (Fe₃O₄), and combinationsthereof. Iron (III) oxide (Fe₂O₃) can be derived from natural sourcessuch as the mineral hematite while iron (II, III) oxide (Fe₃O₄) can bederived from natural sources such as the mineral magnetite. Thecombustion modifier can include 1, 2, 3, 4, 5, or more of theorganometallic soaps. The organometallic soap is soluble in fuelproducts derived from petroleum oil as well as in other hydrocarbonfuels.

In an exemplary embodiment, the organometallic soap can be the reactionproduct of 1,1′-bis(ethenyl-4-pyridyl)-ferrocene and -1,1′-binaphthol.

In one embodiment, the organometallic soap can be diborylated ferroceneonly although the combustion modifier preferably also contains a cerouscompound for increasing the combustion rate of the fuel in the internalcombustion engine. In another embodiment of the composition, thecombustion modifier may include only a single ferric iron-containingorganometallic soap selected from among those described herein.

In another embodiment, the organometallic soap can becerium-2-ethylhexanoate only although the combustion modifier preferablyalso contains a ferric compound for increasing the combustion rate ofthe fuel in the internal combustion engine by preventing theaccumulation of carbon residues on the internal surface of thecombustion chamber of the internal combustion engine. In anotherembodiment of the composition, the combustion modifier may include onlya single cerium-containing organometallic soap selected from among thosedescribed herein.

In another embodiment, the combustion modifier can include a mixture ofone or more ferric compounds selected from among those described hereinand one or more cerous compounds selected from among those describedherein. The combustion modifier may include the ferric compound ormixture of compounds in a range of about 10 to 100 percent by weight orabout 60 to 80 percent by weight and the cerous compound or mixture ofcompounds in a range of about 10 to 100 percent by weight or about 20 to40 percent by weight. The combustion modifier can also include theferric compound or mixture of compounds in a range of about 15 to 85,about 35 to 75, or about 65 to 75 percent by weight and the cerouscompound or mixture of compounds in a range of about 15 to 85, about 25to 65, or about 25 to 35 percent by weight. The combustion rate andcombustion efficiency are most improved when the combustion modifiercontains about 70 percent by weight ferric compound or compounds andabout 30 percent by weight cerous compound or compounds.

In another embodiment, the combustion modifier can include a mixture ofn-butyl ferrocene, 1,1′-dimethyl ferrocene, or benzoyl ferrocene and oneor more cerous compounds selected from among those described herein. Thecombustion modifier may include at least one of n-butyl ferrocene,1,1′-dimethyl ferrocene, or benzoyl ferrocene in a range of about 10 to100 percent by weight or about 60 to 80 percent by weight and the cerouscompound or mixture of compounds in a range of about 10 to 100 percentby weight or about 20 to 40 percent by weight. The combustion modifiercan also include at least one of n-butyl ferrocene, 1,1′-dimethylferrocene, or benzoyl ferrocene in a range of about 15 to 85, about 35to 75, or about 65 to 75 percent by weight and the cerous compound ormixture of compounds in a range of about 15 to 85, about 25 to 65, orabout 25 to 35 percent by weight. The combustion rate and combustionefficiency are most improved when the combustion modifier contains about70 percent by weight of at least one of n-butyl ferrocene, 1,1′-dimethylferrocene, or benzoyl ferrocene and about 30 percent by weight cerouscompound or compounds.

In another embodiment, the combustion modifier can include a mixture ofcerium-2-ethylhexanoate and diborylated ferrocene. In this embodiment,the combustion modifier may include diborylated ferrocene in a range ofabout 10 to 100 percent by weight or about 60 to 80 percent by weightand cerium-2-ethylhexanoate in a range of about 10 to 100 percent byweight or about 20 to 40 percent by weight. The combustion modifier canalso include diborylated ferrocene in a range of about 15 to 85, about35 to 75, or about 65 to 75 percent by weight andcerium-2-ethylhexanoate in a range of about 15 to 85, about 25 to 65, orabout 25 to 35 percent by weight. The combustion rate and combustionefficiency are most improved when the combustion modifier contains about70 percent by weight diborylated ferrocene and about 30 percent byweight cerium-2-ethylhexanoate.

In a preferred embodiment, the combustion modifier can be a mixture ofdiborylated ferrocene and cerium octoate. In this embodiment, thecombustion modifier may include diborylated ferrocene in a range ofabout 10 to 100 percent by weight or about 60 to 80 percent by weightand cerium octoate in a range of about 10 to 100 percent by weight orabout 20 to 40 percent by weight. The combustion modifier can alsoinclude diborylated ferrocene in a range of about 15 to 85, about 35 to75, or about 65 to 75 percent by weight and cerium octoate in a range ofabout 15 to 85, about 25 to 65, or about 25 to 35 percent by weight. Thecombustion rate and combustion efficiency are most improved when thecombustion modifier contains about 70 percent by weight diborylatedferrocene and about 30 percent by weight cerium octoate. This embodimentof the composition is preferred because of the high combustionefficiency and combustion rate achieved by use of the combustionmodifier during testing.

In the most preferred embodiments, the combustion modifier can be amixture of diborylated ferrocene and cerium ammoniate or a mixture ofdiborylated ferrocene and cerium ureate. The mixtures of compoundscontained in these embodiments of the composition may reduce nitrogenoxide emissions produced by combustion of the fuel. These embodiments ofthe composition are most preferred because, during testing, theseembodiments of the combustion modifier achieved the highest combustionefficiency and combustion rates. The combustion modifier may includediborylated ferrocene in a range of about 10 to 100 percent by weight orabout 60 to 80 percent by weight and either cerium ammoniate or ceriumureate in a range of about 10 to 100 percent by weight or about 20 to 40percent by weight. The combustion rate and combustion efficiency aremost improved when the combustion modifier contains about 70 percent byweight diborylated ferrocene and about 30 percent by weight ceriumammoniate or cerium ureate. In other embodiments, the combustionmodifier may include diborylated ferrocene in a range of about 15 to 85,about 40 to 60, about 35 to 75, or about 65 to 75 percent by weight withthe remainder of the composition including either cerium ammoniate orcerium ureate in a range of about 15 to 85, about 40 to 60, about 25 to65, or about 25 to 35 percent by weight.

In an alternate embodiment of the invention, the combustion modifier caninclude a mixture of diborylated ferrocene and both cerium ammoniate andcerium ureate. In this embodiment, the combustion modifier can includediborylated ferrocene in a range of about 10 to 100 percent by weight orabout 60 to 80 percent by weight and a mixture of both cerium ammoniateand cerium ureate in a range of about 10 to 100 percent by weight orabout 20 to 40 percent by weight. The mixture of cerium ammoniate andcerium ureate may contain cerium ammoniate in a range of about 0.001 to99.999 percent by weight and cerium ureate in a range of about 0.001 to99.999 percent by weight. In other embodiments, the combustion modifiercan include diborylated ferrocene in a range of about 15 to 85, about 40to 60, about 35 to 75, or about 65 to 75 percent by weight with theremainder of the composition including a mixture of both ceriumammoniate and cerium ureate in a range of about 15 to 85, about 40 to60, about 25 to 65, or about 25 to 35 percent by weight. The combustionrate and combustion efficiency are most improved when the combustionmodifier contains about 70 percent by weight diborylated ferrocene andabout 30 percent by weight of the mixture of cerium ammoniate and ceriumureate.

Hydrocarbon fuels with which the combustion modifier can be mixedinclude, for example, (1) petroleum-derived fossil fuels such asgasoline, diesel, jet fuel, fuel oil, and kerosene; (2) biofuels such asbioethanol, biodiesel, straight vegetable oils (pure plant oils), andwaste vegetable oils; and (3) combinations thereof.

The combustion modifier may be a solid in the form of a pill, caplet,tablet, powder, bar, block, or amorphous form. The combustion modifiermay also be manufactured as a liquid or gel. In one embodiment, thecombustion modifier can be manufactured to include nanophase particlesof the organometallic soap.

To produce the combustion modifier as a liquid, the organometallic soapcan be dissolved in a solvent blend comprising Solvent 142, dibasicester, and propylene glycol mono-n-butyl ether. Solvent 142 is a heavyhydrotreated petroleum with a flashpoint above 142 degrees Fahrenheit,which includes a mixture of predominantly aliphatic hydrocarbons (forexample, paraffins and cycloparaffins) having hydrocarbon chain lengthspredominantly in the range of C9 through C12. In other embodiments, thesolvent blend may include about 0.1 to 10, about 3 to 7, about 3.5 to 5,or about 4 to 6 percent by weight organometallic soap; about 70 to 90,about 75 to 85, about 77 to 83, or about 80 to 82 percent by weightSolvent 142; about 5 to 15, about 7 to 11, or about 8.5 to 10 percent byweight dibasic ester; and about 1 to 10, about 4 to 6, or about 4.5 to5.5 percent by weight propylene glycol mono-n-butyl ether. In anotherembodiment, the solvent blend may include about 2 to 8 percent by weightorganometallic soap, about 73 to 89 percent by weight Solvent 142, about6 to 12 percent by weight dibasic ester, and about 3 to 7 percent byweight propylene glycol mono-n-butyl ether. In an exemplary embodiment,the blend may include about 4 percent by weight organometallic soap,about 81 percent by weight Solvent 142, about 10 percent by weightdibasic ester, and about 5 percent by weight propylene glycolmono-n-butyl ether.

When produced in tablet form, the active ingredients of the combustionmodifier compositions may be added to a benign hydrocarbon carrier suchas biphenyl, naphthol, beta naphthol, naphthol-2, beta-binaphthol,dicyclopentadiene, or combinations thereof. In exemplary embodiments,the combustion modifiers can contain either beta-binaphthol,dicyclopentadiene, combinations of these two carriers, or either or bothof these carriers in combination with biphenyl, naphthol, beta naphthol,naphthol-2, beta-binaphthol, dicyclopentadiene, or mixtures thereof.

The carrier solvent of the combustion modifiers described herein canalso be diphenyl carbonate, dimethyl carbonate, or combinations thereof.

In another embodiment, the composition for improving the combustionefficiency of an internal combustion engine in combusting hydrocarbonfuels can include a hydrocarbon fuel, a hydrocarbon carrier, and acombustion modifier. The combustion modifier can be the reaction productof 1,1′-bis(ethenyl-4-pyridyl)-ferrocene and -1,1′-binaphthol. Thehydrocarbon carrier can be a compound selected from among one or more ofthe following: biphenyl, naphthol, beta naphthol, naphthol-2,beta-binaphthol, dicyclopentadiene, beta-binaphthol, dicyclopentadiene,and combinations thereof. In exemplary embodiments, the hydrocarboncarrier can be beta-binaphthol, dicyclopentadiene, or combinationsthereof.

Method for Making

The invention features methods for making a combustion modifier that canbe introduced into a fuel tank feeding an internal combustion engine toimprove the efficiency of fuel combustion in the internal combustionengine. In one step of the method, cerium can be mixed and reacted witha synthetic mono-carboxylic acid and with a salt or ester of a secondacid, e.g., 2-ethylhexanoic acid, octoic acid, stearic acid, naphthenicacid, salicylic acid, carbonic acid, or nitric acid. Othercerium-containing compounds can be substituted for the elemental ceriumfor reaction with the mono-carboxylic acid. Other acids and acid blends,including natural mono-carboxylic acids, can also be used to produceless effective combustion modifier compositions.

In another embodiment, a salt of ammonia or urea or an ester of ammoniaor urea may be substituted in place of the salt or ester of the secondacid.

In another embodiment of the method, the second acid, e.g.,2-ethylhexanoic acid, may itself be reacted with cerium in place of thesalt or ester of the second acid. In this embodiment, if the second acidutilized for the reaction with cerium is a carboxylic acid, such as2-ethylhexanoic acid, octoic acid, stearic acid, naphthenic acid, orsalicylic acid, the addition of a mono-carboxylic acid is not required.

The cerium-containing compound and acid are heated and mixed in areactor to form a mixture that may include any of the following cerousorganometallic soap compounds: cerium-2-ethylhexanoate, cerium octoate,cerium stearate, cerium naphthenate, cerium salicylate, ceriumcarbonate, cerium ammoniate, cerium ureate, cerium nitrate, andcombinations thereof.

In another step of the method, a ferric compound (e.g., ferric octoate,ferric-2-ethylhexanoate, ferric stearate, ferric naphthenate, ferricsalicylate, ferric carbonate, diborylated ferrocene, n-butyl ferrocene,1,1′-dimethyl ferrocene, benzoyl ferrocene, or combinations thereof) canbe added to the mixture.

In another step of the method, the mixture is placed under a pressure ofabout 20 inches of mercury (e.g., 15, 18, 19, 19.5, 19.9, 20, 20.1,20.5, 21, 22, or 25 inches of mercury) while heat continues to beapplied. Then, the mixture is placed under a pressure of about 30 inchesof mercury (e.g., 25, 28, 29, 29.5, 29.9, 29.92, 30, 30.1, 30.5, 31, 32,or 35 inches of mercury) while continuing to be heated.

In another step of the method, the mixture undergoes cooling to yield afirst mixture.

In another step of the method, a second mixture can be blended from atleast two dicarboxylic acids.

In another step of the method, the dicarboxylic acids of the secondmixture can be mixed with an alcohol to form a third mixture.

In another step of the method, the third mixture can be heated toproduce a fourth mixture that features dicarboxylic acid esters.

In a final step of the method, the first mixture and the fourth mixturecan be mixed with glycol ether and a solvent to produce a composition.The composition can be used as a combustion modifying fuel additive, asa lubricant, or as both.

Methods for Using

The invention also features methods for improving the efficiency of fuelcombustion in an internal combustion engine. In one embodiment of themethod, one or more of the fuel additive compositions described hereinis introduced into a fuel tank feeding an internal combustion engine. Inan exemplary embodiment of the method, the fuel additive is introducedinto the fuel tank of the internal combustion engine through a fuelline.

In another embodiment of the method, the fuel additive may be premixedwith the hydrocarbon fuel and subsequently introduced into the fuel tankof the internal combustion engine. In another embodiment of the method,the fuel additive may be introduced into the fuel tank, directly intothe combustion chamber, or into both the fuel tank and combustionchamber using a pump or another suitable system for supplying the fueladditive into the internal combustion engine.

The internal combustion engine into which the fuel additive isintroduced can be a reciprocating engine (e.g., a diesel engine, atwo-stroke engine, a four-stroke engine, a five-stroke engine, asix-stroke engine, a crude oil engine, a hot bulb engine, a controlledcombustion engine, or a Bourke engine), a rotary engine (e.g., a Wankelengine), or a continuous combustion engine (e.g., a gas turbine, a jetengine, or a rocket engine). The internal combustion engine may use anysuitable form of combustion such as homogeneous charge spark ignition,stratified charge compression ignition, or homogeneous chargecompression ignition. In one embodiment, the fuel tank into which thecomposition is introduced may be part of a vehicle such as anautomobile, a truck, a motorcycle, an aircraft, a personal watercraft, aboat, a bus, an all-terrain vehicle (ATV), a motorized go-cart, amotorized bicycle, a tractor, a lawn mower, a locomotive, an engineeringvehicle, or a scooter. In another embodiment the fuel tank into whichthe composition is introduced can be part of a generator.

In one embodiment of the method, the fuel additive can be supplied intothe fuel tank in an amount of about 0.01 to 5 grams (e.g., 0.01, 0.05,0.1, 0.5, 1, 1.5, 2, 3, 4, 4.9, 5, or 5.5 grams) per about 20 gallons offuel.

In an exemplary embodiment of the method, the fuel additive is suppliedinto the fuel tank in an amount of about 0.01 to 3 grams (e.g., 0.01,0.05, 0.1, 0.5, 1, 1.5, 2, 2.9, 3, or 3.5 grams) per about 20 gallons offuel.

In a preferred embodiment of the method, the fuel additive is suppliedinto the fuel tank in an amount of about 0.25 to 1 gram (e.g., 0.1, 0.3,0.5, 0.9, 1, 1.1, or 1.5 grams) per about 20 gallons of fuel.

Example 3

By adding the combustion modifying fuel additive to the fuel in anautomobile or other vehicle's internal combustion engine, the combustionefficiency of that internal combustion engine may be significantlyimproved. During testing, diesel fuel was combusted in an internalcombustion engine first without the introduction of the combustionmodifier (the control test shown in FIGS. 1A and 1B) and then with theintroduction of the combustion modifier (the experimental test shown inFIGS. 2A and 2B). The combustion modifier used in the experimental testwas a mixture of 70 percent by weight diborylated ferrocene and 30percent by weight cerium-2-ethylhexanoate. The fuel pounds per hourcombusted by the internal combustion engine was measured and theair/fuel ratio was calculated from the amounts of air and fuel used in agiven time period. The internal combustion engine was operated at thesame horsepower during both tests and measurements were taken atintervals of about one to two minutes.

In the control test, diesel fuel was burned in an internal combustionengine in the absence of the combustion modifier. Approximately 10.8 to11.1 fuel pounds per hour of diesel fuel were combusted by the internalcombustion engine in the absence of the combustion modifier. Theair/fuel ratio for the control test fell within a range of about 52 toabout 54.

In the experimental test, the combustion modifier was added to dieselfuel supplied to an internal combustion engine and the fuel pounds perhour was measured and the air/fuel ratio calculated. As shown in FIGS.1A and 1B, approximately 6.0 to 6.3 fuel pounds per hour were combustedby the internal combustion engine to which the combustion modifier wassupplied. The air/fuel ratio in this experimental test fell within arange of about 99 to about 105. The amount of fuel combusted by theinternal combustion engine in the presence of the combustion modifierwas about 40 percent less than the amount of fuel combusted by theengine during the control test.

In another method of use, one or more of the fuel additive compositionsdescribed herein can be used as a lubricant to lubricate two or moreparts in frictional contact such as, for example, the moving metal partsof an internal combustion engine. In this usage, the composition acts asa lubricating oil.

Other Embodiments

It is to be understood that while the invention has been described inconjunction with the detailed description thereof, the foregoingdescription is intended to illustrate and not limit the scope of theinvention, which is defined by the scope of the appended claims. Otheraspects, advantages, and modifications are within the scope of thefollowing claims.

1. A composition for improving engine performance comprising: a mixtureof esters; glycol ether; and a solvent.
 2. The composition of claim 1,wherein the mixture of esters comprises at least two esters selectedfrom the group consisting of: adipate esters, azelate esters,dodecanedioate esters, sebacate esters, and phthalate esters.
 3. Thecomposition of claim 1, wherein the mixture of esters comprises at leasttwo adipate esters.
 4. The composition of claim 3, wherein the at leasttwo adipate esters comprises an adipic acid ester, a glutaric acidester, and a succinic acid ester.
 5. The composition of claim 1, whereinthe mixture of esters comprises dimethyl adipate, dimethyl gluctorate,and dimethyl succinate.
 6. The composition of claim 1, furthercomprising a smoke suppressant, wherein the smoke suppressant comprisesan organometallic soap.
 7. A composition for improving the combustionefficiency of an internal combustion engine in combusting hydrocarbonfuels, the composition comprising: a hydrocarbon fuel and a combustionmodifier, the combustion modifier comprising an organometallic soap. 8.The composition of claim 7, wherein the organometallic soap is selectedfrom the group consisting of: cerium-2-ethylhexanoate, cerium octoate,cerium stearate, cerium naphthenate, cerium salicylate, ceriumcarbonate, cerium ammoniate, cerium ureate, cerium nitrate, ferricoctoate, ferric-2-ethylhexanoate, ferric stearate, ferric naphthenate,ferric salicylate, ferric carbonate, diborylated ferrocene, n-butylferrocene, 1,1′-dimethyl ferrocene, benzoyl ferrocene, iron (III) oxide(Fe₂O₃), iron (II, III) oxide (Fe₃O₄), and combinations thereof.
 9. Thecomposition of claim 7, wherein the organometallic soap comprises acompound selected from the group consisting of: cerium octoate, ceriumammoniate, cerium ureate, and cerium-2-ethylhexanoate.
 10. Thecomposition of claim 7, wherein the organometallic soap comprisesdiborylated ferrocene.
 11. The composition of claim 7, wherein theorganometallic soap comprises the reaction product of1,1′-bis(ethenyl-4-pyridyl)-ferrocene and -1,1′-binaphthol.
 12. Thecomposition of claim 7, wherein the organometallic soap comprises amixture of diborylated ferrocene and a compound selected from the groupconsisting of: cerium-2-ethylhexanoate and cerium octoate.
 13. Thecomposition of claim 7, wherein the organometallic soap comprises amixture of diborylated ferrocene and a compound selected from the groupconsisting of: cerium ammoniate and cerium ureate.
 14. The compositionof claim 7, wherein the composition further comprises a hydrocarbonfuel.
 15. The composition of claim 7, wherein the smoke suppressantcomprises an iron salt.
 16. A composition for improving the combustionefficiency of an internal combustion engine in combusting hydrocarbonfuels, the composition comprising: a hydrocarbon fuel, a hydrocarboncarrier, and a combustion modifier, the combustion modifier comprisingthe reaction product of 1,1′-bis(ethenyl-4-pyridyl)-ferrocene and-1,1′-binaphthol.
 17. The composition of claim 16, wherein thehydrocarbon carrier comprises a compound selected from among one or moreof the group consisting of: biphenyl, naphthol, beta naphthol,naphthol-2, beta-binaphthol, dicyclopentadiene, beta-binaphthol,dicyclopentadiene, and combinations thereof.
 18. The composition ofclaim 17, wherein the hydrocarbon carrier comprises beta-binaphthol. 19.The composition of claim 17, wherein the hydrocarbon carrier comprisesdicyclopentadiene.
 20. A method comprising the step of: introducing intoan internal combustion engine a hydrocarbon fuel and a fuel additive,the fuel additive comprising: a mixture of esters; glycol ether; and asolvent.
 21. The method of claim 20, wherein the mixture of esterscomprises at least two adipate esters, and wherein the at least twoadipate esters comprises at least two of the following: an adipic acidester, a glutaric acid ester, or a succinic acid ester.
 22. A method ofreducing friction between moving parts comprising: lubricating the atleast two parts that are in frictional contact with a lubricant, thelubricant comprising: a mixture of esters, glycol ether, and a solvent.23. The method of claim 22, wherein the at least two parts comprisemetal parts.
 24. The method of claim 23, wherein the metal partscomprise parts of an internal combustion engine.